Process of preparing a surface-treated positive active material for a lithium secondary battery

Abstract

A process of manufacturing a positive active material for a lithium secondary battery includes adding a metal source to a doping element-containing coating liquid to surface-treat the metal source, wherein the metal source is selected from the group consisting of cobalt, manganese, nickel, and combination thereof; drying the surface-treated metal source material to prepare a positive active material precursor; mixing the positive active material precursor with a lithium source; and subjecting the mixture to heat-treatment. Alternatively, the above drying step during preparation of the positive active material precursor is substituted by preheat-treatment or drying followed by preheat-treatment.

1. A process of preparing a positive active material for a lithium secondary battery, comprising the steps of:
 adding a metal source to a doping element-containing coating liquid including a doping element-containing compound to form a surface-treated metal source having a surface-treatment layer including the doping element-containing compound on a surface of the metal source, wherein the metal source is selected from the group consisting of cobalt, manganese, nickel, and a combination thereof, and the metal source and the doping element are not the same, the doping element being at least one selected from the group consisting of Mg, Al, K, Na, Ca, Si, Fe, Cu, Zn, Ti, Sn, V, Ge, Ga, B, P, Se, Bi, As, Zr, Cr, Sr, Sc, Y, a rare earth element, and a combination thereof; 
 preheat-treating the surface-treated metal source to prepare a positive active material precursor formed of a solid solution of the doping element and the metal source; 
 mixing the positive active material precursor with a lithium source; and 
 heat-treating the mixture to produce the positive active material. 
 
     
     
       2. The process of  claim 1 , wherein the doping element is soluble or suspendable in an organic solvent or water. 
     
     
       3. The process of  claim 1 , wherein the doping element is at least one selected from the group consisting of Mg, Al, Co, Ni, Fe, Zr, Mn, Cr, Sr, V, and a combination thereof. 
     
     
       4. The process of  claim 1 , wherein the metal source is a material including nickel or manganese-nickel. 
     
     
       5. The process of  claim 1 , wherein an amount of the doping-element is in a range from 0.01 to 20 percent by weight of the doping-element-containing coating liquid. 
     
     
       6. The process of  claim 1 , wherein the preheat-treatment step is performed at a temperature in the range from 300° C. to 1000° C., for 1 to 24 hours. 
     
     
       7. The process of  claim 1 , wherein the heat-treatment step comprises the steps of first heat-treating the mixture at 400° C. to 500° C. for 5 to 20 hours, and second heat-treating the mixture at 700° C. to 900° C. for 10 to 30 hours. 
     
     
       8. The process of  claim 1 , wherein the positive active material is a a compound having one of the following formulas (1) to (11):
   Li x Mn 1−y M′ z A 2   (1) 
   Li x Mn 1−y M′ z O 2−a X a   (2) 
   Li x Mn 2−y M′ z A 4   (3) 
   Li x Co 1−y M′ z A 2   (4) 
   Li x Co 1−y M′ z O 2−a X a   (5) 
   Li x Ni 1−y M′ z A 2   (6) 
   Li x Ni 1−y M′ z O 2−a X a   (7) 
   Li x Ni 1−y Co z M′ w A b   (8) 
   Li x Ni 1−y Co z M′ w O 2−b X b   (9) 
   Li x Ni 1−y Mn z M′ w A b   (10) 
   Li x Ni 1−y−z Mn z M′ w O 2−b X b   ( 11), 
 
       wherein
 0.9≦x≦1.1; 0≦y≦0.5; 0≦z≦0.5; 0≦w≦2; 0≦a≦0.5; 0≦b≦2; 
 
       M′ is at least one doping element selected from the group consisting of Mg, Al, Co, Ni, K, Na, Ca, Si, Fe, Cu, Zn, Ti, Sn, V, Ge, Ga, B, P, Se, Bi, As, Zr, Mn, Cr, Sr, and a rare earth element;
 A is at least one element selected from the group consisting of O, F, S, and P; and 
 X is at least one element selected from the group consisting of F, S, and P. 
 
     
     
       9. The process of  claim 1 , wherein an amount of the doping element is in a range from 0.0001 to 20 percent by weight of the positive active material. 
     
     
       10. A process of preparing a positive active material for a lithium secondary battery, comprising the steps of:
 adding a nickel source and a manganese source to a doping element-containing coating liquid including a doping element-containing compound to form a surface-treated metal nickel source and manganese source, the surface-treated nickel source and manganese source having a surface-treatment layer including the doping element-containing compound on a surface of the nickel source and manganese sources the nickel source, the manganese source and the doping element being different from each other, the doping element being at least one selected from the group consisting of Mg, Al, K, Na, Ca, Si, Fe, Cu, Zn, Ti, Sn, V, Ge, Ga, B, P, Se, Bi, As, Zr, Cr, Sr, Sc, Y, a rare earth element, and a combination thereof; 
 preheat-treating the surface-treated nickel source and manganese source to prepare a positive active material precursor formed of a solid solution of the doping element and the nickel source and manganese source; 
 mixing the positive active material precursor with a lithium source; and 
 heat-treating the mixture to heat-treatment to produce the positive active material. 
 
     
     
       11. The process of  claim 2 , wherein the doping element is at least one selected from the group consisting of Mg, Al, K, Na, Ca, Si, Fe, Cu, Zn, Ti, Sn, V, Ge, Ga, B, P, Se, Bi, As, Zr, Cr, Sr, Sc, Y, a rare earth element, and a combination thereof.